Rigid-rod polymers

Abstract

Rigid-rod and segmented rigid-rod polymers, methods for preparing the polymers and useful articles incorporating the polymers are provided. The polymers incorporate rigid-rod backbones with pendant solubilizing groups attached thereto for rendering the polymers soluble.

We claim: 
     
       1. A soluble rigid rod polymer having repeat units of the formula: ##STR12## wherein R 1  is a solubilizing side group having molecular weight of from about 15 to about 300, and wherein the intrinsic viscosity of said polymer is greater than about 3 deciliters/gram when measured at 40° C. in a solvent selected from the group consisting of 0.05M lithium bromide in N-methylpyrrolidinone, N-methylpyrrolidinone, dimethylacetamide, phenylether, m-cresol, sulfuric acid, anisole, 5% N-methylpyrrolidinone/95% CHCl 3 , and chlorobenzene. 
     
     
       2. The polymer of claim 1 where at least about 30% of the monomer units bear a solubilizing side group. 
     
     
       3. The polymer of claim 1 where R 1  is: ##STR13## and wherein X is selected from the group consisting of hydrogen, amino, methylamino, dimethylamino, benzoyl, hydroxy, methoxy, phenoxy, --SC 6  H 5 , and --OCOCH 3 . 
     
     
       4. The polymer of claim 1 where R 1  is: ##STR14## and wherein X is selected from the group consisting of methyl, ethyl, phenyl, benzyl, F, and CF 3 , and n is 1, 2, 3, 4, or 5. 
     
     
       5. The polymer of claim 1 wherein R 1  is --CR 5  R 6  Ar where Ar is aryl, and R 5  and R 6  are independently selected from the group consisting of H, methyl, F, C1 to C20 alkoxy, and OH or R 5  and R 6  taken together as bridging groups are selected from the group consisting of --OCH 2  CH 2  O--, --OCH 2  CH(CH 2  OH)O--, OC 6  H 4  O--, --OC 6  H 10  O-- and --OCH 2  CHR 3  O-- where R 3  is selected from the group consisting of alkyl and aryl. 
     
     
       6. The polymer of claim 1 wherein R 1  is --(CO)X and X is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4-pyridyl, --CH 2  C 6  H 5 , --CH 2  CH 2  C 6  H 5 , 1-naphthyl and 2-naphthyl. 
     
     
       7. The polymer of claim 1 wherein R 1  is --SO 2  X and X is selected from the group consisting of phenyl, tolyl, 1-naphthyl, 2-naphthyl, methoxyphenyl, and phenoxyphenyl. 
     
     
       8. The polymer of claim 1 wherein R 1  is --NR 5  R 6  and wherein R 5  and R 6  are independently selected from the group consisting of hydrogen, methyl, ethyl, phenyl, and --COCH 3  or R 5  and R 6  taken together as bridging groups are selected from the group consisting of --CH 2  CH 2  OCH 2  CH 2  --, --CH 2  CH 2  CH 2  CH 2  CH 2  -- and --CH 2  CH 2  CH 2  CH 2  --. 
     
     
       9. The polymer of claim 1 wherein R 1  is --N═CR 5  R 6  and wherein R 5  and R 6  are independently selected from the group consisting of --H, --CH 3 , --CH 2  CH 3 , phenyl, tolyl, methoxyphenyl, benzyl, aryl, and C1 to C22 alkyl, or R 5  and R 6  taken together as bridging groups are selected from the group consisting of --CH 2  CH 2  OCH 2  CH 2  --, --CH 2  CH 2  CH 2  CH 2  CH 2  -- and --CH 2  CH 2  CH 2  CH 2  --. 
     
     
       10. A free-standing film comprising a polymer of claim 1. 
     
     
       11. A fiber comprising a polymer of claim 1. 
     
     
       12. A molded article comprising a polymer of claim 1. 
     
     
       13. A coating composition comprising a polymer of claim 1. 
     
     
       14. The polymer of claim 1 where the intrinsic viscosity of said polymer is greater than about 3.5 deciliters/gram when measured at 40° C. in a solvent selected from the group consisting of 0.05M lithium bromide in N-methylpyrrolidinone, N-methylpyrrolidinone, dimethylacetamide, phenylether, m-cresol, sulfuric acid, anisole, 5% N-methylpyrrolidinone/95% CHCl 3 , and chlorobenzene. 
     
     
       15. The polymer of claim 1 where the intrinsic viscosity of said polymer is greater than about 5 deciliters/gram when measured at 40° C. in a solvent selected from the group consisting of 0.05M lithium bromide in N-methylpyrrolidinone, N-methylpyrrolidinone, dimethylacetamide, phenylether, m-cresol, sulfuric acid, anisole, 5% N-methylpyrrolidinone/95% CHCl 3 , and chlorobenzene. 
     
     
       16. The polymer of claim 1 where the intrinsic viscosity of said polymer is greater than about 7.2 deciliters/gram when measured at 40° C. in a solvent selected from the group consisting of 0.05M lithium bromide in N-methylpyrrolidinone, N-methylpyrrolidinone, dimethylacetamide, phenylether, m-cresol, sulfuric acid, anisole, 5% N-methylpyrrolidinone/95% CHCl 3 , and chlorobenzene. 
     
     
       17. The polymer of claim 1 where the weight average molecular weight of said polymer as measured by gel permeation chromatography against polystyrene standards is greater than about 218,000. 
     
     
       18. The polymer of claim 1 where the weight average molecular weight of said polymer as measured by gel permeation chromatography against polystyrene standards is greater than about 500,000. 
     
     
       19. The polymer of claim 1 wherein the tensile modulus of unoriented 25 micron film of said polymer is greater than about one million pounds per square inch. 
     
     
       20. A soluble rigid-rod copolymer having repeat units of the formula: ##STR15## wherein R 1  is independently selected from H or a solubilizing side group having molecular weight of from about 15 to about 300, wherein the intrinsic viscosity of said copolymer is greater than about 3 dl/g when measured at 40° C. in a solvent selected from the group consisting of 0.05M lithium bromide in N-methylpyrrolidinone, N-methylpyrrolidinone, dimethylacetamide, phenylether, m-cresol, sulfuric acid, anisole, 5% N-methylpyrrolidinone/95% CHCl 3 , and chlorobenzene, wherein at least about 30% of the monomer units bear a solubilizing side group, and wherein a portion of the monomer units are absent a solubilizing side group.